Fast yellow dyes and process of making same.



ED STATES PATENT GFFICE.

RUDOLF SCH'ULE, OF FRANKIORT-ON-THE-MAIN, GERMANY, ASSIGNOR TO CASSE-LLACOLOR COMPANY, A CORPORATION'OF- NEW YORK.

FAST YELLOW EYES AND PROCESS OF MAKING SAME.

No Drawing.

T all whom it may concern:

Be it known that I, RUDo F SoHiiLn, Ph.D., a subject of the SwissRepublic, and residing at \Valdschmidtst-rasse 26, Frankfort-on-theMain, Germany, have invented certain Fast Yellow Dyes and Process ofMaking Same, of which the following is a full description.

According to my invention a tetrazotized base of thediaminotriphenylmethane group is coupled with two molecules ofavpyrazolonesulfonic acid and thereby yellow to orange wool dyestuffsare produced which are distinguished by their good solubility and theirexcellent fastness to light, and

.The process of manufacture is illustrated by the following examples:

Example I: A solution of 27.4 kilos diaminotriphenylmethane in about 300liters water and 60 liters hydrochloric 'acid of 20 Be. are well cooled;then a solution of 13.8 kilos sodium nitrite is slowly added. The diazocompound is stirred into a solution of 57.7 kiloso-chlor-p-sulfophenylmethylpyrazolone to which are added 4% kilos sodiumcarbonate in 500 liters water. In order to complete the reaction, thesolution is gradually heated to about 35-40 C. and then allowed to standfor some hours. From the solution thus obtainedthe dyestuff is separatedin the usual manner by salting out. The yellowish greenish solution ofthe dyestuii is not changed in shade by hydrochloric acid but it isrendered somewhat lighter by caustic soda. The color- Speeification ofLetters Patent.

The symmetrical dyestuff obtained from one molecule of.diamino-o-o-tolylphenylmethane, one molecule of(-)-sulfo-o-tolylmethylpyrazolone and one molecule ofp-sulfophenylmethylpyrazolone is represented by the following graphicalformula:

ing matter dissolves in concentrated sulfuric acid with a yellow color.

Example II: A solution of 34.3 kilos diamino-o-o-dichlortriphenylmethane(from benzaldehyde and o-chloranilin) in 500 liters water and (30 litershydrochloric acid of B6. is tetrazotized at 0 C. with a solution of 13.8kilos sodium nitrite. It is combilled as before with 53.6 kilos (5)sulfo-otolyhnethyl-pyrazolone in the presence of ll kilos sodiumcarbonate dissolved in 500 liters water. The dyestufi is similar to theone described above, dyeing wool a clear greenish-yellow shade.

Example III: 37.6 kilos m-nitrophenyldiaminodixylyhnethane (obtainedfrom mnitrobenzaldehyde and two molecules pxylidin) are dissolved in asolution of 20 liters hydrochloric acid of 20: in 500 liters water,cooled with ice to 0 C., and

Patented Feb. 15, 1916.

Application filed March 17, 1913. Serial No. 754,822.

charged with 40 liters more hydrochloric acid. A solution of 13.8 kilossodium nitrite is added while the temperature is kept at G. Then a coldsolution of 57.7 kilos o-sulfc-p-chlorphenylmethylpyrazolone and l-ikilos sodium carbonate in 500 liters water is allowed. to run into thetetrazo solution. The formation of the dyestulf is completed by raisingthe temperature of the solution slowly to 40 C. The dyestutf dyes wool areddish-yellow shade. I

Example IV: 36.2 kilos of the condensation product of benzaldehyde andaminocrekilos sodium nitrite.

solmethylether are dissolved .in 600 liters -water and 20 litershydrochloric acid of 20? B., and tetrazotized at 0 G. with 13-8 Bycombination with a solntionof 50.8 kilos p-sulfophenylmethylpyra'zoloneand 14 kilos sodium carbonate in about 500 liters water cooled down to 0C., a reddish orange dyestulf is obtained.

Example V A dyestulf may be produced from two differentpyrazolonesulfonic acids as follows: A solution of 30.2 kilos diami-.no-di-o o-tolylphenylmethane in 200 liters water and litershydrochloric acid is tetrazotized .in the usual manner with 13.8

kilos sodium nitrite. This solution is neutrahzed by the addition of asolution of 58 kllOS sodium acetate. An intermed ate com- 7 pound isformed by allowing the. solution of bonate The dyestufi dyes Wool 26.8kilos (5) -sulfo-o-tolyhnethylpyrazolcne to run slowly into the solutionof the tetrazo compound, until an excess of the latter has disappeared.The intermediate compound thus obtained is allowed to run into asolution of kilos p sulfophenylmethylpyrazo lone and 4A kilos sodiumcarbonate in 400 liters water, cooled down to 0 C. Thedyestuff isseparated by salting out.

Example VI: The tetrazo compound obtained in the usual manner from 37.6kilos diaminotriphenylmethanenronosulof the fonic acid formed frombenzaldehyde monosulfonic acid and anilin) is combined in the presenceof sodium acetate with 173 kilos phenylmethylpyrazolone; dissolved -Withcaustic soda and water. The intermediate compound which is sparinglysoluble in Water is allowed to run into a solution of 29 kilos-o-chl0r-p-sulfoplienylmethylpyrazolone rendered alkaline with sodiumcar.- pure gr een ish yellow shades.

Example VII: 43.4: kilos of thedisulfonic acid obtained bytreating'diaminotriphenylmethane with sulfuric acid 6f 66 Be, at a lowtemperature, are tetra'Z-otized in the usual manner. By combin n'g thistetrazo compound with 34.8 kilo phenylmethylpyrazolone in thepresence'of sodium carbonate a yellowish orange dyestufl' is ob tained.

Having now particularly described and ascertained the nature of my saidinvention and in what manner the same is to be performed, I declare thatwhat I claim is:

l. The process of producing fast dyestufis by combining the tetrazocompound obtained by tetrazotizing a diaminot'riarylme thane base withtwo molecules of an aryl-' methylpyrazolonesulfonic acid.

2. The process of producingfast azo dyes by combining the tetrazocompound ob tained by tetrazotizing a diaminotriarylmethane base withtwo molecules of two different arylmethylpyrazolonesulfonic acids. I

3. The process of producing fast azo dyes by combining the tetrazocompound obtained by tetrazotlzing a diaminotriphenylmethanesulfonicacid. with two'molecules of i an aryhnethylpyrazolone.

a. The process of producing fast azo dyes by combining the tetrazocompound obtained. by tetrazotizing a diaminotriaryh Inethanesulfon'icacid with one molecule of an arylmethylpyrazolone and one molecule ofanarylmethylpyrazolonesulfonic acid.

5. As new articles of manufacture the hereinbefore described'new azodyes derived fromtetrazotized diaminotriarylmethane compounds andarylmethylpyrazolone com-' pounds, these new are dyes dyeing animalfibers in an' acid bath greenish yellow to orange yellow shades of greatfastness to milling and being in the dry state yellow to' brownpowders,dissolving readily in water with a yellow color, which is not altered bythe addition of hydrochloric acid, and which is rendered somewhat palerby the addition of caustic soda, and which yield on being signed'my namethis 4th. -dayof March 1913, in the presence of-two subscribingwitnesses.

DR. RUDOLF soHtniE. Witnesses JEAN Grimm; CARL GRUND.

